Barrier article and method

ABSTRACT

A barrier article and a method of making and using the barrier article are provided. The barrier article includes a base layer; an adhesive layer supported on a first surface of the support layer; and a barrier layer supported on a second surface of the support layer, opposite the adhesive layer.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a non-provisional application claiming priority toprovisional U.S. patent application Ser. No. ______, filed ______, andhereby incorporates by reference and claims benefit thereto.

BACKGROUND

1. Technical Field

The invention includes embodiments that relate to a barrier article. Theinvention includes embodiments that relate to method of making and/orusing a barrier article.

2. Discussion of Related Art

Barbed wire and barbed metal tape have been used as barriers to preventor reduce access to defined areas. The barbed wire and barbed metal tapemay be wound and unwound so that, when deployed, a substantially linear,spiral and/or helical barrier may be formed. Deployed wires and tapessometimes may be fixed in place using, for example, pegs and fasteners.

It would be desirable to have a barrier article having improvedproperties, such as, for example, differing fastening mechanisms,differing deployment methods, differing manufacturing processes,differing modes of function, and the like. It would be desirable to havediffering methods for making and using the same.

SUMMARY

The invention has embodiments that relate to a barrier article that mayinclude one or more of barrier properties, intrusion detectionproperties, and deterrent properties.

The invention has embodiments that relate to a barrier system. Theinvention has embodiments that relate to an intrusion detection system.The invention has embodiments that relate to a personal deterrentsystem.

In one embodiment, a barrier article may include a base layer; anadhesive layer supported on a first surface of the support layer; and abarrier layer supported on a second surface of the support layer,opposite the adhesive layer.

In one embodiment, a method may include securing a plurality of barrierstructures to a base layer, each of the barrier structures having anextended end spaced from the base layer; and may further includesecuring an adhesive layer to a surface of the base layer opposite theextended end of the barrier structures.

Other embodiments may become apparent to one of ordinary skill in therelevant field of art in response to a review of the specification anddrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram showing a cross-sectional side view of abarrier article comprising an embodiment in accordance with theinvention;

FIG. 2 is a schematic diagram showing configurations of barrierstructures disposed in a barrier layer according to embodiments of theinvention;

FIG. 3 is a schematic diagram showing a frangible barrier structuredisposed in a barrier layer according to embodiments of the invention;

FIG. 4 is a schematic diagram showing a barrier article comprising anembodiment of the invention.

DETAILED DESCRIPTION

The invention includes embodiments that may relate to a barrier articleand/or a defensive article or barrier article. The invention includesembodiments that may relate to a method of making and/or using thearticles.

Approximating language, as used herein throughout the specification andclaims, may be applied to modify any quantitative representation thatcould permissibly vary without resulting in a change in the basicfunction to which it is related. Accordingly, a value modified by a termor terms, such as “about” and “substantially”, are not to be limited tothe precise value specified.

An article 100 comprising an embodiment according to the invention isshown in FIG. 1. The article 100 may include a base layer 110, anadhesive layer 120 secured to a first surface 122 of the base layer 110,and a defensive or barrier layer 130 secured to a second surface 132 ofthe base layer 110, opposite the adhesive layer 120. The barrier layer130 may include an exposed or exposable surface 134, and the adhesivelayer may include a contact surface 136.

The base layer 110 in the embodiment illustrated in FIG. 1 may be formedof a flexible, metal-fiber reinforced thermoplastic polymer having arelatively high glass transition temperature (Tg). The base layer 110may be about 50 micrometers thick and may include filler materials thatincrease toughness and heat resistance. The adhesive layer 120 may beformed of thermosetting polymeric adhesive having very high adhesionstrength and a high glass transition temperature. The adhesive layer 120may be about 50 micrometers thick, and may include filler materials thatincrease toughness and heat resistance. The barrier layer 130 may beformed of metal and defines clusters of sharp projections that extendaway from the base layer 110 at differing angles to the sharp free end.Some of the projections may have barbed ends.

A base layer, in accordance with embodiments of the invention, mayinclude one or more of thermoplastic polymer, thermoset polymer, metal,cellulosic material, and the like. A base layer may be a film, a sheet,or stock, and may be substantially uniform in thickness or may bethicker in someplace, and relatively thinner in other places. Films,sheets, and stock may be differentiated from each other based on averagethickness. Films may have a thickness in a range of less than about 25micrometers (10 mils), sheets may have a thickness in a range of fromabout 25 micrometers (10 mils) to about 250 micrometers (100 mils), andstock may be anything thicker than sheets.

A base layer may include one or more polymeric material or polymer, andmay further include one or more of filler, additive, or pigment. Asuitable polymer may include a thermoplastic material, a thermosettingmaterial, or both, and may include a synthetic polymer, a naturallyoccurring polymer, or both.

Suitable binders, resins, monomers, or polymers (hereinaftercollectively “polymers”) for use in forming a base layer may includethermoplastic material, thermoset material, or a combination of both. Inone embodiment, a polymer may include one or more of polyacrylamide,polyacrylate, polyamide, polycarbonate, epoxy, polyester, polyether,ionomer, polyimide, polyolefin, polystyrene, polyurethane, polyvinyl,silicone, polysiloxane, or norbornene polymer.

Suitable polyamide polymers may include polymers commercially availablefrom EMS American Grilon Inc., (Sumter, S.C.) under the tradenameGRIVORY such as CF₆S, CR-9, XE3303 and G-21. GRIVORY G-21 may be anamorphous nylon copolymer having a glass transition temperature (Tg) of125 degrees Celsius, a melt flow index of 90 g/10 min and an elongationat break of 15. Elongation at break may be determined with reference toASTM D638, which is hereby incorporated by reference in its entirety.GRIVORY CF₆₅ may be a nylon 6/12 film grade polymer having a meltingpoint of 135 degrees Celsius, an MFI of 50 g/10 min, and an elongationat break in excess of 350%. GRILON CR9 may be a nylon 6/12 film gradepolymer having a melting point of 200 degrees Celsius, an MFI of 200g/10 min, and an elongation at break at 250%. GRILON XE 3303 may be anylon 6.6/6.10 film grade polymer having a melting point of 200 degreesCelsius, an MFI of 60 g/10 min, and an elongation at break of 100%.Suitable polyamide polymers may include those available from, forexample, Union Camp, Inc. (Wayne, N.J.) under the UNI-REZ product line,and dimer-based polyamide polymers available from Henkel of America,Inc. (Gulph Mills, Pa.) under the VERSAMID product line. Suitablepolyamides may include those produced by condensing dimerized vegetableacids with hexamethylene diamine.

Suitable polycarbonates may include those commercially available fromthe CALIBRE, from Dow Chemical Co. (Midland, Mich.), LEXAN, from GEPlastics (Pittsfield, Mass.), and MAKROLON, from Bayer Corporation(Pittsburgh, Pa.). Other suitable polycarbonates may be obtained by areaction of bisphenol A and carbonyl chloride in an interfacial process.Suitable molecular weight may be less than about 20,000, in a range offrom about 20,000 to about 35,000, or greater than about 35,000; and asuitable melt flow rate may be less than about 5 g/10 min, in a range offrom about 5 to about 20 g/10 min, or greater than about 20 g/10 min.

Suitable polyesters may include one or both of polyethyleneterephthalate (PET) or PETG (PET modified with cyclohexanedimethanol).Polyesters may be obtained commercially, such as KODAR 6763, a PETGavailable from Eastman Chemical (Rochester, N.Y.), or SELAR PT-8307 aPET available from DuPont Corporation (Wilmington, Del.). Other suitablepolyesters may be prepared from various glycols or polyols and one ormore aliphatic or aromatic carboxylic acids.

An ionomer is a polyolefin containing ionic bonded molecular chains. Inone embodiment, ionomers may be used. Suitable ionomers may includeionomeric ethylene copolymers such as SURLYN 1702 or SURLYN 1706, bothavailable from DuPont, and which may include an inter-chain ionic bondbased on a zinc salt of ethylene methacrylic acid copolymer.

Suitable polyolefins may include one or more of: polyethylene orpolypropylene, or a polymer or copolymer having ethylene or propyleneunits; oxygenated ether, oxygenated butadiene, or oxygenated isoprene;halogenated ether, halogenated butadiene, or halogenated isoprene;butadiene derivatives, such as butadiene-styrene,butadiene-isoprene-styrene, butadiene-vinyl-styrene,butadiene-vinyl-toluene, butadiene-isoprene-toluene, and the like;polyacrylate or polymethacrylate, or a polymer or copolymer havingacrylic or methacrylic units; acrylonitrile; vinylic hydrocarbonpolymers reacted with unsaturated materials such as the reaction productof maleic acid with styrene, or maleic anhydride with styrene; and,polymeric, rubber-like, elastomeric latex polymers and copolymers ofethylenically unsaturated polymers and polymers obtainable in stableaqueous latex form. In one embodiment, a halogenated polyolefin mayinclude fluoroethylene, such as polytetrafluoroethylene.

Suitable polyolefins may be characterized as having a melt index or meltflow rate of less than about 10, in a range of from about 10 to about20, or greater than about 30 as determined by ASTM Test Method 1238,which is hereby incorporated by reference in its entirety. A polyolefinmay include polymers and copolymers of ethylene, propylene, 1-butene,and the like, and may further include blends and mixtures of suchpolymers and copolymers.

Suitable polyethylene polyolefins may include low, medium, or highdensity polyethylene, or combinations of two or more thereof. A lowdensity range for a polyethylene may in a range of from less than about0.910 grams per cubic centimeter (g/cm³) to about 0.925 g/cm³, a mediumdensity range may be from about 0.925 g/cm³ to about 0.940 g/cm³, and ahigh density range may be from about 0.940 g/cm³ to greater than about0.965 g/cm³. A low density polyethylene (LDPE) may be REXENE 1017, whichis commercially available from Huntsman Corporation (Houston, Tex.).

Suitable propylene polyolefins may include polypropylene homopolymer, ora copolymer, such as propylene-ethylene or propylene-1-butene copolymer.Blends of polypropylene and polyethylene with each other, or blends ofeither or both of them with a polypropylene-polyethylene copolymer maybe used. The polyolefin film forming materials may have a highpropylenic content, either polypropylene homopolymer orpropylene-ethylene copolymers or blends of polypropylene andpolyethylene with low ethylene content, or propylene-1-butene copolymersor blend of polypropylene and poly-1-butene with low butene content.

Suitable propylene homopolymers may have a melt flow rate (MFR) fromabout 0.5 to about 20 as determined by ASTM Test D 1238, condition L. Inone embodiment, propylene homopolymers may have a melt flow rate (MFR)or a melt flow index (MFI) of less than about 4 grams per 10 minutes(g/10 min), and in a range of from about 4 g/10 min to about 8 g/10 min,from about 8 g/10 min to about 10 g/10 min, or greater than about 10g/10 min. Here and throughout the specification and claims, rangelimitations may be combined and interchanged, for example, the above MRFor MFI range may be from less than about 4 g/10 min to greater thanabout 10 g/10 min. As used herein, MFR and MFI may be determined withreference to DIN 53735, which is hereby incorporated by reference in itsentirety. Suitable propylene homopolymers may have a density less thanabout 0.8 g/cm³, in a range of from about 0.8 g/cm³ to about 0.9 g/cm³,or greater than about 0.9 g/cm³. Commercially available propylenehomopolymers may include 5A97, available from Union Carbide Corporation(Danbury, Conn.), which has an MFR of 12.0 g/10 min and a density of0.90 g/cm³; DX5E66, also available from Union Carbide, has an MFI of 8.8g/10 min and a density of 0.90 g/cm³; and WRD5-1057 from Union Carbidehaving an MFI of 3.9 g/10 min and a density of 0.90 g/cm³.

Suitable polystyrene may include homopolymers and/or copolymers ofstyrene, and may include substituted styrene such as alpha-methylstyrene. Examples of suitable styrene copolymers and terpolymers mayinclude one or more of acrylonitrile-butene-styrene (ABS),styrene-acrylonitrile copolymers (SAN), styrene butadiene (SB),styrene-maleic anhydride (SMA), or styrene-methyl methacrylate (SMMA),and the like.

A suitable polymer may include one or more polyurethane. Suitablepolyurethanes may include diphenylmethane diisocyanate, methylenediethyl diisocyanate, isocyanurate. Suitable polyurethanes may includealiphatic polyurethanes. Other suitable polyurethanes may includearomatic polyurethanes. Polyurethanes having a cyclic moiety may besuitable, and combinations of one or more of aliphatic, aromatic, orcyclic may be suitable also.

In one embodiment, a vinyl polymer, such as alkylene vinyl acetatepolymers (e.g., EVA polymer) may be used. Suitable commerciallyavailable vinyl polymers may include ESCORENE UL-7520, a copolymer ofethylene with 19.3% vinyl acetate; and NUCRELL 699), an ethylenecopolymer containing 11% of methacrylic acid. ESCORENE and NUCRELL areavailable from Exxon Mobil Corporation (Irving, Tex.) and DuPontCorporation, respectively. In addition, suitable vinyl polymers mayinclude one or more of vinyl-based and/or vinylidene-based polymers orcopolymers. In one embodiment, a vinyl polymer may include one or moreof polyvinyl chloride, polyvinyl butyral, polyvinyl acetal, polyvinylacetoacetal, polyvinylidene fluoride, polyvinylidene chloride, polyvinylalcohol, or polyethylene vinyl alcohol, and the like, and combinationsof two or more thereof.

Suitable polysiloxanes may be entirely inorganic, may have an inorganicbackbone with organic side groups, or may be formed from organicmodified precursors. In one embodiment, a suitable siloxane may includean alkoxy moiety, a glycidyl or epoxy moiety, a cyano or cyanato moiety,an amino moiety, a mercapto moiety, or a combination of moieties thatinclude two or more thereof. Suitable organic side groups may includefrom about 1 to about 100 carbon atoms and may have an aliphatic, cyclicand/or aromatic character. Suitable organic modified precursors for thepolysiloxane include acrylic, urethane and epoxy functional polymers oroligomers.

A suitable polysiloxane may be formed using a sol-gel process or acondensation reaction, particular from silane precursors. A siloxaneaccording to one embodiment may be air-dried at room temperature, or maybe heat dried, or heat cured. In one embodiment, the siloxane may bepolymerized or cured by exposure to radiation. Suitable radiation mayinclude one or more of ultraviolet, infrared, electron beam, and/orvisible light. Cross linking or curing of the siloxane material maydepend on the choice of siloxane material and the functionality thereof.In one embodiment, the siloxane may be chemically initiated to formlinkages. Commercially available cross linking or curing methods may bedetermined with reference to the selection of siloxane material, and mayinclude ambient cure systems, thermal cure systems, radiation curesystems, moisture cure systems, and one and two part curing agent orcross link initiating systems.

In one embodiment, a silane and/or polysilane may have an alkoxy moiety,such as mono, di, tri, and tetralkoxy functionality. For example,preselected alkoxy silanes may be mixed with water to hydrolyze thealkoxysilane into silanol and alcohol. In one embodiment, a suitablesilane may include a glycidyl moiety, an amino moiety, a cyano orcyanato moiety, a mercapto moiety, or a combination of moieties thatinclude two or more thereof. In one embodiment, the silane may includeone or more of glycidoxyproyl trimethoxy silane, 1,2 bis(triethoxysilyl)ethane, gamma-aminopropyl triethoxy silane, mercaptoproyl trimethoxysilane, polydimethylsilane, vinyl silane, aminopropyl silane, epoxysilane, or vinyl triactosilane. A suitable silane may include anon-hydrolyzable functional group. Such groups may include amino, vinyl,ureido, epoxy, mercapto, isocyanato, methacrylato, vinylbenzene andsulfane functional groups. Examples of suitable silanes may includevinyltrimethoxysilane, bis-triethoxysilylpropyl tetrasulfane, aminotrimethoxysilane, and ureidopropyl trimethoxysilane. Other examples ofsuitable silanes may include 1,2 bis-(triethoxysilyl) ethane,1,2-bis-(trimethoxysilyl) ethane, 1,6-bis-(trialkoxysilyl) hexane,1,2-bis-(triethoxysilyl) ethylene, or bis-triethoxysilylpropyltetrasulfane.

Suitable polysiloxanes may include ADSIL AD-65 or ADSIL AD-95, which arecommercially available from Adsil Corporation (Palm Coast, Fla.). In oneembodiment, a suitable silicon-containing material may include SDC TECHMP-100, which is commercially available from SDC Technologies, Inc.(Anaheim, Calif.). A suitable silane may include an ECOSIL brandproduct, which may be obtained from Epro Services, Inc. (Derby, Kans.).

In one embodiment, a suitable polymer for use in a base layer mayinclude one or more of urea formaldehyde, phenolformaldehyde, phenolicpolymers, carbon-carbon composites, or fibrin polymers, and the like.

In one embodiment, the metal base layer may be a foil, a plate, or ametal film or sheet. Suitable metal for the base layer may includealuminum, antimony, arsenic, barium, bismuth, beryllium, boron, cadmium,calcium, cerium, cesium, chromium, cobalt, copper, germanium, gold,holmium, iridium, iron, lanthanum, lead, lithium, magnesium, manganese,mercury, molybdenum, neodymium, nickel, niobium, osmium, platinum,phosphorous, potassium, praseodymium, rhenium, rubidium, selenium,silicon, silver, sodium, steel, strontium, tantalum, tellurium,thallium, thorium, tin, titanium, tungsten, uranium, vanadium, zinc, orzirconium; or oxides thereof; or mixtures or alloys thereof.

In one embodiment, the ceramic or cermet base layer may be a foil, aplate, or a metal film or sheet. In one embodiment, the base layer maybe a ceramic coated metal object. Cermet includes materials that havemetal bonded ceramic particles fired at an elevated temperature, andceramic includes non-metallic minerals fired at an elevated temperatureand refers also to enamel.

Suitable ceramic and cermet materials may include aluminum, antimony,arsenic, barium, bismuth, beryllium, boron, cadmium, calcium, cerium,cesium, chromium, cobalt, copper, germanium, gold, holmium, Iron,lanthanum, lead, lithium, magnesium, manganese, molybdenum, neodymium,nickel, niobium, osmium, platinum, phosphorous, potassium, praseodymium,rhenium, rubidium, selenium, silicon, silver, sodium, strontium,tantalum, tellurium, tin, titanium, tungsten, uranium, vanadium, zinc,or zirconium; or alloys thereof; or halides, sulfides, nitrides, oxidesor carbides thereof.

In one embodiment, suitable ceramics may include one or more of aluminumtriethoxide, aluminum isopropoxide, aluminum sec-butoxide, aluminumtri-t-butoxide, magnesium trifluoroacetylacetonate, magnesium methoxide,magnesium ethoxide, titanium methoxide, titanium ethoxide, titaniumisopropoxide, titanium propoxide, titanium butoxide, titaniumethylhexoxide, titanium (triethanolaminato) isopropoxide, titaniumbis(ethyl acetoacetato) diisopropoxide, titanium bis(2,4-pentanedionate)diisopropoxide, zirconium ethoxide, zirconium isopropoxide, zirconiumpropoxide, zirconium sec-butoxide, zirconium t-butoxide, aluminumdi-s-butoxide ethylacetonate, calcium methoxyethoxide, calciummethoxide, magnesium methoxyethoxide, copper ethoxide, coppermethoxyethoxyethoxide, antimony butoxide, bismuth pentoxide, chromiumisopropoxide, tin ethoxide, zinc methoxyethoxide, titanium n-nonyloxide,vanadium tri-n-propoxide oxide, vanadium triisobutoxide oxide, ironethoxide, tungsten ethoxide, samarium isopropoxide, iron isopropoxide,cobalt methoxyethoxide, or lanthanium methoxyethoxide.

Suitable base layers, generally, may be flexible, rigid, or brittle. Inone embodiment, a flexible base layer may be conformable, and in anotherembodiment may be non-conformable. A conformable base layer may beelastic or may be inelastic, and may, for example, stretch toaccommodate surface irregularities during application to the surface,stretch to accommodate trapped material such as air, water or dirtduring application to a surface, and/or stretch to accommodate movementin a substrate to which it is applied where the movement may result fromthermal expansion, vibration, and the like.

A rigid base layer may be, in one embodiment, similar to floorcoverings, such as tiles or linoleum, in configuration, installation anduse. In another embodiment, a rigid base layer may be plate-like insofaras substrate surface areas may be covered using a plurality of barrierarticle units that are plate-like, and which provide a relativelyincreased resistance to removal and/or tamper attempts. In oneembodiment, a rigid base layer may be formed from metal, ceramic, orboth. In an alternative embodiment, a base layer, particularly a rigidbase layer, may further include anchor structures to assist or enhancean adhesive layer in securing a barrier article to a substrate surface.Suitable anchor structures may include fasteners, tacks, pegs, anchors,screws, barbs, and the like, and combinations of two or more thereof.

An adhesive layer for use in embodiments of the invention may include acurable adhesive, a structural adhesive, a pressure sensitive adhesive,and the like, or a combination of two or more thereof. In oneembodiment, an adhesive layer may include an emulsion-based adhesive ora solvent-based adhesive. In one embodiment, the adhesive may be ahot-melt adhesive. In one embodiment, the adhesive may be apressure-activated adhesive. A suitable adhesive for use in an adhesivelayer may include one or more of hot-melt adhesives, moisture curableadhesives, pressure-activated adhesives, and radiation curableadhesives, and the like. As used herein, a structural adhesive, whenfully adhered to a substrate, has an adhesive strength equal to orgreater than the cohesive strength of the adhesive, the substrate, orboth. A pressure-activated adhesive may have a curing agent or initiatoradmixed within, and may respond to pressure by releasing the curingagent or initiator and thereby begin a curing process of the adhesive.Solvent-based adhesives may include those adhesives that form adhesiveproperties in response to an evaporation or loss of a solvent initiallycontained in the adhesive. A hot melt adhesive may flow and liquefyunder high temperatures, and may form adhesive properties upon cooling.

In one embodiment, a method of making a suitable adhesive may include:(1) preparing a polymer mixture comprising one or more polymerizablepolymers; (2) polymerizing the polymer mixture to form a polymerizedmixture; (3) modifying the polymerized mixture with a modifying polymer;and (4) neutralizing the resulting modified mixture.

A suitable adhesive layer may have a patterned thickness, or asubstantially uniform thickness, of less than about 25 micrometers, in arange of from about 25 to about 35 micrometers, from about 35micrometers to about 50 micrometers, or greater than about 50micrometers.

In one embodiment, an adhesive layer may be continuous. In oneembodiment, an adhesive layer may be discontinuous. A discontinuousadhesive layer define a pattern of areas having adhesive and other areasthat are adhesive-free, or substantially adhesive-free. Alternatively oradditionally, an adhesive layer may include two or more adhesives havingdiffering properties. For example, a first adhesive with a relativelystrong adhesive strength may be disposed in some areas, but a secondadhesive with a relatively weak adhesive strength may be disposed inother areas. In one embodiment, first and second adhesive materials aredisposed at different heights relative to each other. A weak adhesivemay protrude further than a strong adhesive, so that the weak adhesivemay contact a substrate first during an application. In such asituation, the weak adhesive layer may provide initial tack forpositioning, but may allow slight movement of the laminate to allowpositioning adjustments prior to the stronger adhesive forming arelatively more permanent bond. Such an arrangement may facilitateslideability, repositioning, smoothing, and/or air egress.

A suitable adhesive layer may include two or more differing adhesives.In one embodiment, an adhesive layer may include a pressure sensitiveadhesive (PSA), and may further include one or more of a moistureactivatable adhesive, a hot-melt adhesive, a two-component adhesive asdescribed herein, a solvent or water-based adhesive, or a heatactivatable adhesive layer. In one embodiment, differing adhesive arecommixed or commingled, and in one embodiment, differing adhesives maybe substantially unmixed, but in the same adhesive layer. In oneembodiment, an adhesive layer may be discontinuous, and differingadhesive materials may be disposed throughout portions of thediscontinuous adhesive layer to provide differing adhesivefunctionality.

In one embodiment, a curing adhesive may be a radiation-initiatedadhesive. Suitable radiation-initiated adhesives may include ultraviolet(UV) curable adhesives and electron beam (EB) curable adhesives, also,heat and infrared (IR) curable adhesives may be included. Suitablechemical-initiated adhesives may include

A suitable curing adhesive may include chemically activated two-partadhesives, which may by cured by contact with a surface primer oradhesion initiator. Suitable two-component adhesives for use with anadhesion initiator may include a thermosetting, anaerobically curablepolymeric polymer system that may contact the adhesion initiator andcure in response to contacting the same. Suitable adhesion initiatorsmay include an organocopper catalyst, such as LOCTITE 7469 PRIMER, whichis commercially available from Henkel Loctite Corp. (Rocky Hill, Conn.).In other embodiments, suitable alternative adhesion initiators mayinclude other metallic catalysts, such as organo-iron catalysts,zirconium complexes (such as K-KAT XC-9213), metal chelates (such asNACURE XC-9206), and antimony-based catalysts (such as NACURE XC-7231),all of which are commercially available from King Industries, Inc.(Norwalk, Conn.). Other suitable adhesion initiators in alternativeembodiments may include nitrogen and sulfur based catalysts.

A suitable adhesive for use in an adhesive layer may include one or morepolymer selected from acrylates, amides, acrylonitriles, carbonate,cyanate esters, cyanurates, ethylene-vinyl acetate, epoxy,fluoroplastics, ionomers, methyl methacrylates, non-ethylenic olefinpolymers (linear or branched), nylon, olefins, polyester, styrene,styrene-maleic anhydride, sulfones, styrene-acrylonitrile, urethanes,and combinations of two or more thereof. In one embodiment, an adhesivemay include an ethylenically unsaturated polymer that is capable ofundergoing polymerization or copolymerization. As used herein, binder,resin, monomer, and unsaturated polymer may be collectively referred tocollectively as a polymerized end product or “polymer”.

As noted above, a suitable adhesive may include an acrylate polymer. Asuitable acrylate may include those derived from ethylene methacrylicacid, ethylene methyl acrylate, ethylene acrylic acid and ethylene ethylacrylate. Additional suitable acrylic polymers may include ethoxylatedtrimethylol propane triacrylate, trimethylol propane trimethacrylate,dipentaerythritol monohydroxy pentacrylate, pentaerythritol triacrylate,ethoxylated trimethylol propane triacrylate, 1,6-hexanedioldiacrylate,neopentyl glycol diacrylate, pentaerythritol tetraacrylate, 1,2-butyleneglycoldiacrylate, trimethylopropane ethoxylate trimethacrylate, glycerylpropoxylate trimethacrylate, trimethylolpropane trimethacrylate,dipentaerythritol monohydroxy pentamethacrylate, tripropylene glycoldimethacrylate, neopentyl glycol propoxylate dimethacrylate,1,4-butanediol dimethacrylate, polyethylene glycol dimethacrylate,triethyleneglycol dimethacrylate, butylene glycol dimethacrylate,ethoxylated bisphenol A dimethacrylate, and the like, and combinationsof two or more thereof.

In one embodiment, an acrylic polymer may be formed from alkylene glycoldiacrylate polymers. Such alkylene glycol diacrylate polymers may beselected from mono-, di-, tri-, tetra- and polyethylene glycoldimethacrylate and corresponding diacrylates; dipentamethylene glycoldimethacrylate; tetraethylene glycol dichloroacrylate; diglyceroldiacrylate; diglycerol tetramethacrylate; butylene glycoldimethacrylate; neopentyl glycol diacrylate; and trimethylopropanetriacrylate. In one embodiment, suitable amino polymers may includesubstituted and/or unsubstituted aminoalkyl acrylates, hydrochloridesalts of amino polymers, and methacrylates, such as beta-aminoethylacrylate, beta-amino ethyl ethacrylate, dimethyl aminomethylacrylate, beta-methyl amino ethylacrylate, and dimethyl aminomethylmethacrylate.

In one embodiment, an alkyl acrylate and/or methacrylate may includefrom about 4 carbon atoms to about 10 carbon atoms, from about 10 carbonatoms to about 20 carbon atoms, or more than about 20 carbon atoms. Anacrylate may be copolymerized with a modifying polymer (for example, asecond acrylic ester) and/or polymers with predetermined functionalgroups (e.g., acrylic, methacrylic, itaconic acids, and amides thereof).Suitable polymers may include butyl acrylate, 2-ethylhexyl acrylate, andiso-octyl acrylate.

In one embodiment, an acrylate polymer may include further one or morefunctional oxiranyl (oxirane) groups. In one embodiment, an acrylatepolymer may include further one or more functional urethane groups, suchas in a urethane-acrylate-capped prepolymer, which may be based onpolybutadiene polyols, or based on polyamines and acrylates.

In one embodiment, a monofunctional acrylate ester (esters containingone acrylate group) may be used. A suitable acrylate ester may have arelatively polar moiety. Polar groups may be selected from labilehydrogen, heterocyclic ring, hydroxy, amino, cyano, and halogen polargroups; examples may include cyclohexyl methacrylate, tetrahydrofurfurylmethacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate,t-butylaminoethyl methacrylate, cyanoethylacrylate, and chloroethylmethacrylate. Acrylate esters may be incorporated as reactive diluentscapable of copolymerizing with various other polymerizable materials.

Suitable amides of carboxylic acids may include unsubstituted amidessuch as methacrylamide, alpha-substituted acrylamides, and n-substitutedamides obtained by the reaction of the amides of the aforementionedcarboxylic acids with an aldehyde (e.g., formaldehyde). In oneembodiment, n-substituted amides may include one or more of n-methylolacrylamide, n-methylol methacrylamide, alkylated n-methylol acrylamides,and n-methylol methacrylamides (e.g., n-methyoxymethylacrylamide andn-methoxy methyl methacrylamide). Suitable nitriles, that is,ethylenically unsaturated carboxylic acids, may include acrylonitrile,alpha-chloroacrylonitrile, and methacrylonitrile.

Suitable polyepoxide resins may be solid or liquid at room temperature.Suitable epoxides may include linear polymers having terminal epoxidegroups (e.g., the diglycidyl ether of bisphenol-A), polymers havingpendent epoxy groups (e.g., polyglycidyl ethers of phenolic novolakcompounds), or both.

In one embodiment, an adhesive may include one or more of aromaticepoxy, aliphatic epoxy, or cycloaliphatic epoxy, and may have multipleepoxy functional groups. Suitable aromatic polyepoxides may include twoor more 1,2-cyclic ethers. Such compounds may be aromatic orheteroaromatic, or a combination thereof. Aromatic polyepoxide may beincluded in an adhesive layer to increase the glass transitiontemperature (Tg) of a cured adhesive layer and to provide heatresistance.

Suitable aromatic epoxides (i.e., compounds containing at least onearomatic ring structure, e.g., a benzene ring, and at least two epoxidegroups) may include one or more of polyglycidyl ethers of polyhydricphenols, such as Bisphenol-A or Bisphenol-F type resins and theirderivatives, aromatic polyglycidyl amines (e.g., polyglycidyl amines ofbenzenamines, benzene diamines, naphthylenamines, or naphthylenediamines), polyglycidyl ethers of phenol formaldehyde resole or novolakresins; resorcinol diglycidyl ether; polyglycidyl derivatives offluorene-type resins; and glycidyl esters of aromatic carboxylic acids,e.g., phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester,trimellitic acid triglycidyl ester, and pyromellitic acid tetraglycidylester.

In one embodiment, an aromatic polyepoxide may include polyglycidylethers of polyhydric phenols, such as the series of diglycidyl ethers ofBisphenol-A, commercially available from Resolution PerformanceProducts, Inc. (Houston, Tex.), for example, under the tradedesignations “EPON 828” and “EPON 1001F” and the series of diglycidylethers of Bisphenol-A and Bisphenol F and their blends, commerciallyavailable from Resolution Performance Products, Ltd. (Pernis, TheNetherlands), for example, under the trade designations “EPIKOTE 232”and “EPIKOTE 1001”. Other useful commercially available aromaticepoxides include the “DER” series of Bisphenol epoxides and “DEN” seriesof epoxy novolak resins, available from Dow Chemical Corporation(Midland, Mich.); diglycidyl ether of fluorene Bisphenol, available fromResolution Performance Products, under the trade designation “EPON HPTResin 1079”; a triglycidyl derivative of p-aminophenol, commerciallyavailable from Ciba Performance Polymers, Inc. (Brewster, N.Y.), underthe trade designation “MY 0500”; a tetraglycidyl derivative of methylenedianiline, commercially available from Ciba Performance Polymers, underthe trade designation “MY 720”; and a polyfunctional aromatic epoxideresin commercially available from Resolution Performance Products underthe trade designation “EPON SU-8.” Flame retardant epoxides may also beused, for example, the flame retardant brominated Bisphenol-A diglycidylether, commercially available from Dow Chemical Corporation, under thetrade designation “DER 580”. The term “derivative” as used herein withreference to thermosetting materials refers to a base molecule withadditional substituents that do not interfere substantially with thethermosetting curing reaction of the base molecule.

In one embodiment, an adhesive may include one or more ofN,N″-diglycidyl-p-aminophenyl-glycidyl ether, triglycidyl p-aminophenolderived resins, 1,3,5-triglycidyl isocyanurate,tetraglycidylmethylenedianiline, or a glycidyl ether derivative of anovolac resin.

Suitable methacrylic acid esters may include one or more C1-C17 alkylmethacrylates. In one embodiment, methacrylic esters may include methylmethacrylate, ethyl methacrylate, isopropyl methacrylate,n-butylmethacrylate, isobutylmethacrylate, hexyl acrylate, 2-ethylhexylmethacrylate, t-butyl methacrylate, 3,3-dimethylbutyl methacrylate, andlauryl acrylate.

Suitable adhesives may include block copolymers of vinyl aromatichydrocarbons and conjugated dienes. Block copolymers may be diblock,triblock, multiblock, starblock, polyblock or graftblock copolymers.Throughout the specification and claims, the term ‘block’, as used indiblock, triblock, multiblock, polyblock, and graft or grafted block,refers to the polymer building block used to make the block copolymer.Such block copolymers may have structures represented by the formulaeAB, ABA, ABAB, BAB, ABBA, and the like, where A may be a hard orcrystalline polymer block of, for example, a vinyl aromatic hydrocarbonor a conjugated diene/vinyl aromatic hydrocarbon tapered copolymerblock; and B may a rubbery polymer block of, for example, a conjugateddiene. Suitable multi block copolymers may include linear and/orradially symmetric, and/or linear and/or radially asymmetric copolymers.

In one embodiment, an adhesive may include rubber based elastomermaterials such as linear, branched, graft or radial-block copolymersrepresented by the diblock structures A-B, the triblock A-B-A, theradial or coupled structures (A-B)n, and combinations of these where Arepresents a hard thermoplastic phase or block which is non-rubbery orglassy or crystalline at room temperature but fluid at highertemperatures, and B represents a soft block which is rubbery orelastomeric at service or room temperature. These thermoplasticelastomers may include from about 75% to about 95% by weight of rubberysegments and from about 5% to about 25% by weight of non-rubberysegments.

The non-rubbery segments or hard blocks include polymers of mono- andpolycyclic aromatic hydrocarbons, and more particularlyvinyl-substituted aromatic hydrocarbons which may be monocyclic orbicyclic in nature. The rubbery blocks or segments are typically polymerblocks of homopolymers or copolymers of aliphatic conjugated dienes.Rubbery materials such as polyisoprene, polybutadiene, and styrenebutadiene rubbers may be used to form the rubbery block or segment. Therubbery segments include polydienes and saturated olefin rubbers ofethylene/butylene or ethylene/propylene copolymers. The latter rubbersmay be obtained from the corresponding unsaturated polyalkylene moietiessuch as polybutadiene and polyisoprene by hydrogenation thereof.

Suitable block copolymers may be prepared using one or more ofsequential addition of polymer, incremental addition of polymer, orcoupling techniques. Tapered copolymer blocks can be incorporated intomultiblock copolymers, for example, by copolymerizing a mixture ofconjugated diene and vinyl aromatic hydrocarbon polymers utilizing adifference in copolymerization reactivity rates.

In one embodiment, a conjugated diene may be utilized to prepare anadhesive polymer and/or copolymer. Suitable conjugated dienes may from 4carbon atoms to about 6 carbon atoms, or from about 6 carbon atoms toabout 10 carbon atoms, or more than about 10 carbon atoms. Examples ofsuitable conjugated dienes may include one or more of 1,3 butadiene, 2methyl 1,3 butadiene (isoprene), 2,3 dimethyl 1,3 butadiene,chloroprene, 1,3 pentadiene, 1,3 hexadiene, and the like. In oneembodiment, an adhesive polymer may include a conjugated diene selectedfrom isoprene, 1,3 butadiene, or both.

Examples of suitable vinyl aromatic hydrocarbons which may be utilizedto prepare copolymers may include styrene and/or a substituted styreneor styrene derivative. Suitable styrene derivatives may includeo-methylstyrene, p-methylstyrene, p-tert butylstyrene,1,3-dimethylstyrene, alpha methylstyrene, beta methylstyrene,p-isopropylstyrene, 2,3 dimethylstyrene, o-chlorostyrene,p-chlorostyrene, o-bromostyrene, 2-chloro-4-methylstyrene, and the like.In one embodiment, an adhesive polymer may include styrene.

A number average molecular weight of suitable block copolymers, forexample prior to hydrogenation, may be less than about 20,000, in arange of from about 20,000 to about 40,000, from about 40,000 to about300,000, from about 300,000 to about 500,000, or greater than about500,000. An average molecular weight of the individual blocks within acopolymer may pre-selected with reference to application specificcriteria. In one embodiment, a vinyl aromatic block may have a numberaverage molecular weight of less than about 2000, in a range of fromabout 2000 to about 4000, from about 4,000 to about 60,000, from about60,000 to about 125,000, or greater than about 125,000. A conjugateddiene block may have number average molecular weight of less than about10,000, in a range of from about 10,000 to about 35,000, from about35,000 to about 150,000, from about 150,000 to about 450,000, or greaterthan about 450,000.

In one embodiment, a block copolymer may contain a ratio of conjugateddiene to vinyl aromatic hydrocarbons having less than about 40 weightpercent, from about 40 weight percent to about 50 weight percent, orgreater than about 50 weight percent of conjugated diene relative tovinyl aromatic hydrocarbon.

Prior to hydrogenation, a vinyl content of a conjugated diene portionmay be less than about 10 weight percent, in a range of from about 10weight percent to about 80 weight percent, or may be greater than about80 weight percent. Vinyl content may be less than about 25 weightpercent, in a range of from about 25 weight percent to about 35 weightpercent, from about 35 weight percent to about 55 weight percent, or maybe greater than about 55 weight percent. In one embodiment, anelasticity of a modified block copolymer may be controlled bypre-selecting a vinyl content thereof. Vinyl content of the blockcopolymer may be determined, for example, using nuclear magneticresonance.

Examples of suitable diblock copolymers (AB-type) may include one ormore of styrene-butadiene (SB), styrene isoprene (SI), and hydrogenatedderivatives thereof. Examples of suitable triblock polymers (ABA-type)may include one or more of styrene butadiene styrene (SBS), styreneisoprene styrene (SIS), styrene-butadiene-isoprene (SBI), ormethylstyrene-isoprene-methylstyrene (MIM). Upon hydrogenation of theSBS copolymers comprising a suitable mixture of 1,4 and 1,2 isomers, astyrene-ethylene-butylene styrene (SEBS) block copolymer is obtained.Hydrogenation of an SIS polymer may yield a suitablestyrene-ethylene-propylene-styrene (SEPS) block copolymer. VECTOR 4111is a suitable SIS block copolymer (ABA-type), which is commerciallyavailable from Dexco Corporation (Houston Tex.). In one embodiment, aconjugated diene portion of the block copolymer may be about 90%saturated, or may be from about 90% to about 95% saturated, or may bemore saturated than about 95%.

In one embodiment, the selectively hydrogenated block copolymer may havea structure as shown below in formula (I):B_(n)(AB)_(o)A_(p)  (I)where n=0 or 1; o=1 to 100; p=0 or 1; each B prior to hydrogenation maybe a polymerized conjugated diene hydrocarbon block, and may have anumber average molecular weight in a range of from about 20,000 to about450,000; and, each A may be a polymerized vinyl aromatic hydrocarbonblock, and may have a number average molecular weight in a range of fromabout 2000 to about 115,000. In one embodiment, blocks of A mayconstitute about 5% to about 95% by weight of a copolymer; and, anunsaturation of block B may be less than about 10% of an originalunsaturation level. In other embodiments, unsaturation of block B may bereduced, relatively, upon hydrogenation to less than 5% of the originalvalue, and the average unsaturation of the hydrogenated block copolymermay be reduced to less than 20% of the original value.

Suitable commercially available maleated and selectively hydrogenatedcopolymers of styrene and butadiene include KRATON brand products, whichare commercially available from Kraton Polymers (Houston, Tex.). KRATOND, G, FG, IR and Liquid polymers include styrenic block copolymers(SBCs) based on feedstocks of styrene, butadiene and isoprene. In oneembodiment, styrene may be polymerized with butadiene, isoprene, orboth. KRATON D polymers may be elastic and flexible. KRATON G polymersmay be SBCs with a hydrogenated midblock, and may be elastic, flexible,and include enhanced oxidation and weather resistance, higher servicetemperatures and a relatively increased processing stability. KRATON FGpolymers may have improved adhesion to polar substrates such as metalsand nylons. KRATON IR polymers may include anionically polymerizedpolyisoprene rubbers, which may yield polyisoprene rubbers with arelatively low gel content and chemical impurity level. Other suitableblock copolymers may be commercially available from Nippon Zeon Co.(Tokyo, Japan), for example, QUINTAC 3530, which may include a linearstyrene-isoprene-styrene (SIS) block copolymer.

In one embodiment, a hydrocarbon polymer may include one or more ofstyrene compounds (e.g., styrene, carboxylated styrene, or alpha-methylstyrene), ethylene, propylene, butylene, and conjugated dienes (e.g.,butadiene, isoprene and copolymers of butadiene and isoprene).

Examples of suitable vinyl and vinylidene halides may include one ormore of vinyl chloride, vinylidene chloride, vinyl fluoride andvinylidene fluoride. In one embodiment, a vinyl ester may includealiphatic vinyl esters. Suitable vinyl esters may include one or more ofvinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinylisobutyrate, vinyl valerate, and vinyl caproate. Suitable vinyl estersmay include allyl esters of saturated monocarboxylic acids, such asallyl acetate, allyl propionate, and allyl lactate. Suitable vinylethers may include one or more of methylvinyl ether, ethylvinyl ether,and n-butylvinyl ether. Suitable vinyl ketones may include one or moreof methylvinyl ketone, ethylvinyl ketone, and isobutyl vinyl ketone.

Suitable ethylenically unsaturated polymers may include alkyl esters anddialkyl esters; ethylenically unsaturated carboxylic acids; nitriles,vinyl and vinylidene halides, and amides of unsaturated carboxylicacids; mono- and polyunsaturated hydrocarbon polymers; vinyl esters(e.g., vinyl esters of C1 to C6 saturated monocarboxylic acids); vinylethers; and amino polymers. Ethylenically unsaturated monocarboxylicacids may include methacrylic acid, ethacrylic acid, and crotonic acid.Ethylenically unsaturated dicarboxylic acids may include maleic acid,fumaric acid, itaconic acid, and citraconic acid. Suitable ethylenicallyunsaturated tricarboxylic acids may include aconitic acid, andhalogen-substituted derivatives thereof (e.g., alphachloracylic acid),and the anhydrides of these acids (e.g., maleic anhydride and citraconicanhydride). Suitable dialkyl esters of ethylenically unsaturateddicarboxylic acids may include one or more of dimethyl maleate, diethylmaleate, dibutyl maleate, dioctyl maleate, diisooctyl maleate, dinonylmaleate, diisodecyl maleate, ditridecyl maleate, dimethyl fumarate,diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dioctyl fumarate,diisooctyl fumarate, didecyl fumarate, dimethyl itaconate, diethylitaconate, dibutyl itaconate, and dioctyl itaconate.

As noted hereinabove, an adhesive may include a hot melt adhesive. Asuitable hot melt pressure sensitive adhesive may include one or more ofHM-1597, HL-2207-X, HL-2115-X, HL-2193-X, which are commerciallyavailable from H.B. Fuller Company, (St. Paul, Minn.); or H2187-01,which is commercially available from Ato Findley, Inc. (Wauwatusa,Wis.). Other suitable hot melt pressure sensitive adhesives may includethose commercially available from Century Adhesives Corporation(Columbus, Ohio).

The adhesive compositions also may include one or more additives.Suitable additives may include a toughening agent, tackifying polymer,wax, wetting agent, antioxidant, heat stabilizer, light stabilizer,ultraviolet light absorber, filler, colorant, pigment, opacifier,antiblocking agent, reinforcing agent, processing acid, fire retardantadditive, biocide, anti-mildew agent, defoamer, flow agent, elastomer,plasticizer, thixotropic agent, suspension agent, water repellantadditive, modifier, curing agent, hardening agent, flexibilizer,catalyst, and the like. In one embodiment, an adhesive may include acuring agent or hardener.

A suitable toughening agent may include insoluble in situ polymerizedelastomeric particles that are formed from amine terminated polyethers,for example, diprimary amine endcapped poly(tetramethyleneoxides). Othersuitable toughening agents may include amine-terminatedbutadiene/nitrile rubbers, carboxyl-terminated butadiene/nitrilerubbers, and core shell materials.

Suitable tackifying polymers may include a solid tackifier polymercomponent. A solid tackifier may have a softening point above 80 degreesCelsius. When the solid tackifier polymer component is present, theadhesive compositions may include from about 40 to about 80% by weightof a thermoplastic elastomer component and from about 20% to about 60%by weight, and in one embodiment from about 55 to about 65% by weight ofa solid tackifier polymer component. A solid tackifier may reduce themodulus of the mixture to build tack or adhesion. Also, solid tackifiers(particularly the higher molecular weight solid tackifiers may be lesssensitive to migration into the polymer base layer, and this isdesirable Suitable tackifying polymers may have an average molecularweight of less than about 2000, about 2000, or greater than about 2000;and, may have a dispersity (Mw/Mn) of about 1, in a range of from about1 to about 2, from about 2 to about 3, or greater than about 3.

Suitable solid tackifier polymers may include polyterpene polymers,hydrocarbon polymers, synthetic tackifier polymer, rosin, hydrogenatedrosin, rosin esters, and the like. A suitable polyterpene polymer mayinclude ZONATAC brand polymers from Arizona Chemical Company, Inc.(Jacksonville, Fla.). A suitable petroleum hydrocarbon polymer mayinclude ESCOREZ brand polymer from Exxon Chemical Company. Acommercially available synthetic tackifier polymer may include WINGTACK95 available from Goodyear Corporation (Akron, Ohio).

The adhesive compositions may contain inorganic fillers and otherorganic and inorganic additives to provide desired properties. Suitablefillers may include one or more of calcium carbonate, titanium dioxide,silicon carbide, metal particles, fibers, and the like. Flame retardantsmay include one or more of ethylene bis pentabromo biphenyl, brominatedbisphenol, halogenated metal oxide, or antimony trioxide.

Suitable modifiers may include one or more vinyl ester polymers such asstyrene, vinyl 2-ethylhexanoate, vinyl caprate, vinyl laurate, vinylpelargonate, vinyl hexanoate, vinyl propionate, vinyl decanoate, andvinyl octanoate. In one embodiment, a modifier may be present in anamount in the range of from about 0.1 weight percent to about 1 weightpercent (based on the total weight of all the polymerizable polymers inthe polymer mixture), from about 1 weight percent to about 20 weightpercent, from about 20 weight percent to about 50 weight percent, orgreater than about 50 weight percent.

A suitable modifier may include a liquid rubber. A suitable liquidrubber may have an average molecular weight of less than about 5,000, ina range of from about 5,000 to about 20,000, or greater than about20,000. Incorporation of liquid rubbers in amounts of less than 5 weightpercent, or in a range of from about 5 weight percent to about 10 weightpercent, based on the overall weight of the adhesive formulation, mayaid to form an adhesive which may be coextrudable with a base layer. Amodulus of an adhesive may be relatively lowered by the incorporation ofone or more liquid rubber. In one embodiment, incorporation of a liquidrubber into an adhesive may produce an adhesive having increased tackand/or adhesion, and may lower the glass transition temperature of theadhesive. Liquid block copolymers, such as liquid styrene-isoprene blockcopolymers may be used, for example, a liquid polyisoprene obtained bydepolymerization of high molecular weight polyisoprene. An example of acommercially available depolymerized high molecular weight polyisoprenemay be ISOLENE D-400 from Elementis Performance Polymers, (Belleville,N.J.). Other suitable liquid rubbers which may be incorporated into anadhesive may include one or more of liquid styrene-butadiene rubbers,liquid butadiene rubbers, ethylene-propylene rubbers, and the like.

A suitable curing agent may serve to crosslink a two-part adhesive. Inone embodiment, a curing agent may be a multifunctional organic compoundcapable of reacting with functional groups located within the adhesive.Suitable curing agents may include amines, amides, phenols, thiols,carboxylic acids, carboxylic anhydrides, and mixtures thereof. In oneembodiment, a curing agent may include polyoxyalkyleneamine. In oneembodiment, a curing agent may include one or more anhydrides, such ascis-1,2-cyclohexane dicarboxylic anhydride, methyl hexohydropthalicanhydride, and mixtures thereof. A curing agent may be added to anadhesive in an amount of less than about 1 weight percent, in a range offrom about 1 weight percent to about 2 weight percent, from about 2weight percent to about 5 weight percent, from about 5 weight percent toabout 10 weight percent, or greater than about 10 weight percent.

A hardener may improve a curing reaction. Suitable hardeners may includeamine hardeners, such as isophorone diamine, triethylene tetraamine,diethylene triamine, amino ethylpiperazine, 1,2- and 1,3-diaminopropane,2,2-dimethyl propylenediamine, 1,4-diaminobutane, 1,6-diaminohexane,1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononae,1,12-diaminododecane, 4-azaheptamethylene diamine,N,N-bis(3-aminopropyl) butane-1,4-diamine, cyclohexane diamine,dicyandiamine, diamide diphenyl methane, diamide diphenyl sulfonic acid(amine adduct), 4,4-methylene dianiline, diethyltoluene diamine,m-phenylene diamine, melamine formaldehyde, tetraethylene pentamine,3-diethylamino propylamine, 3,3-imino bis propylamine,2,4-bis(p-aminobenzyl) aniline, tetraethylene pentamine, 3-diethylaminopropylamine, 2,2,4- and 2,4,4-trimethylhexa methylene diamine, 1,2- and1,3-diamino cyclohexane, 1,4-diamino-3,6-diethyl cyclohexane,1,2-diamino-4-ethyl cyclohexane, 1,4-diamino-3,6-diethylcyclohexane,1-cyclohexyl-3,4-dimino-cyclohexane, 4,4-diamino dicyclo hexylmethane,4,4-diamino dicyclo hexylpropane, 2,2-bis(4-aminocyclohexyl) propane,3,3-dimethyl-4,4-diamino dicyclohexyl methane, 3-amino-1-cyclohexaneaminopropane, 1,3- and 1,4-bis(aminomethyl) cyclohexane, m- andp-xylylene diamine, and mixtures thereof. In one embodiment, an aminehardeners includes melamine formaldehyde. A hardening agent may be addedto an adhesive in an amount of less than about 1 weight percent, in arange of from about 1 weight percent to about 2 weight percent, fromabout 2 weight percent to about 5 weight percent, from about 5 weightpercent to about 10 weight percent, or greater than about 10 weightpercent.

Suitable flexibilizers may include one or more of silicone polymeradditives, including fumed and unfumed silica; alumina polymeradditives, including fumed and unfumed alumina; polysulfide rubbers; andmixtures of two or more thereof. Flexibilizers may be added to anadhesive in an amount of less than about 1 weight percent, in a range offrom about 1 weight percent to about 2 weight percent, from about 2weight percent to about 5 weight percent, from about 5 weight percent toabout 10 weight percent, or greater than about 10 weight percent.

Suitable catalysts may include substances that contain an unshared pairof electrons in an outer orbital, including Lewis Bases such as tertiaryamines, imidazoles, and imidazolines. In one embodiment, a catalyst mayinclude one or more of 2-ethyl-4-methyl-imidazole, N-(3-aminopropyl)imidazole, 2-phenyl-2-imidazoline, and mixtures of two or more thereof.A catalyst may be added to an adhesive in an amount of less than about 1weight percent, in a range of from about 1 weight percent to about 2weight percent, from about 2 weight percent to about 5 weight percent,from about 5 weight percent to about 10 weight percent, or greater thanabout 10 weight percent.

In one embodiment, an adhesive may have a glass transition temperature(T_(g)) (measured by differential scanning calorimetry) in a range ofless than about 0 degrees Celsius, less than about −10 degrees Celsius,or in a range of from about −30 degrees Celsius to about −10 degreesCelsius. In one embodiment, an adhesive may have a glass transitiontemperature in a range of from about 0 degrees Celsius to about 20degrees Celsius, or in a range of from about 20 degrees Celsius to about50 degrees Celsius, or higher.

In one embodiment, an adhesive may have an adhesion strength that isequal to or greater than the cohesive strength of the adhesive, asubstrate to which the adhesive layer is secured, or both. Lap sheartests conducted using steel to steel one inch lap shears with both 0 milgaps and 5 mil gaps for the bond-line, and pulled according to ASTM 700,which is incorporated by reference, at room temperature, at 50 degreesCelsius and at 100 degrees Celsius. Results are reported in pounds persquare inch (PSI) required to break the lap shear.

In one embodiment, an adhesive may have lap shear test adhesivestrengths at room temperature of less than 1000 PSI, in a range of fromabout 1000 PSI to about 1500 PSI, from about 1500 PSI to about 2000 PSI,from about 2000 PSI to about 2500 PSI, from about 2500 PSI to about 3000PSI, or greater than about 3000 PSI. In one embodiment, an adhesive mayhave lap shear test adhesive strengths at about 50 degrees Celsius ofless than 1000 PSI, in a range of from about 1000 PSI to about 1500 PSI,from about 1500 PSI to about 2000 PSI, from about 2000 PSI to about 2500PSI, from about 2500 PSI to about 3000 PSI, or greater than about 3000PSI. In one embodiment, an adhesive may have lap shear test adhesivestrengths at about 100 degrees Celsius of less than 1000 PSI, in a rangeof from about 1000 PSI to about 1500 PSI, from about 1500 PSI to about2000 PSI, from about 2000 PSI to about 2500 PSI, from about 2500 PSI toabout 3000 PSI, or greater than about 3000 PSI.

A barrier layer according to embodiments of the invention may include aplurality of barrier structures that each may define a point, a sharpedge, a spike, a barb, a hook, and the like, combinations thereof, or aplurality of one or more thereof. In one embodiment, however, a barrierstructure may be dull, rounded, or not sharp, particularly when hollow,as described further hereinbelow. Generally, each of a plurality ofbarrier structures may function to puncture, cut, tear, snag, and thelike at one or more free ends.

Each of a plurality of barrier structures may secure to a base layer atone or more secured ends. Accordingly, in one embodiment a suitablebarrier structure may define a cantilever, having a fixed end secured toa base layer, and a free end facing outward from the barrier article andending in a sharp point. To reduce or eliminate the ability of defeatinga barrier article having a cantilever barrier structure, a combinationof differing barrier structures may be employed in combination. Toprevent defeat by an overlaying of a barrier article with a heavycovering, for example, a puncture type barrier structure may be used; acaltrop type barrier structure may be used, a springing concertina typebarrier structure may be used, active barrier structures (describedfurther hereinbelow) may be used, and the like, and combinationsthereof.

Barrier structure free ends may extend from a base layer surface by alength that may be less than about 0.5 centimeter, in a range of fromabout 0.5 centimeter to about 1 centimeters, from about 1 centimeters toabout 2.5 centimeters, from about 2.5 centimeters to about 5centimeters, from about 5 centimeters to about 7.5 centimeters, fromabout 7.5 centimeters to about 10 centimeters, or greater than about 10centimeters. In one embodiment, barrier structures may havesubstantially the same length. In one embodiment, barrier structures ofa plurality have differing lengths relative to each other.

A barrier structure may be substantially linear, may be curved, or maybe angled along its length. In one embodiment, a barrier structure loopsfrom a base layer back to the base layer, and may make one or more loopsalong its length. Suitable barrier structures may be oriented relativeto a plane defined by a base layer to which they are secured. Suitableorientations may include 90 degrees, in a range of from about 90 degreesto about 80 degrees, from about 80 degrees to about 70 degrees, fromabout 70 degrees to about 55 degrees, from about 55 degrees to about 45degrees, from about 45 degrees to about 25 degrees, or less than about25 degrees. Further, barrier structures may be aligned relative to eachother in substantially the same direction, or, alternatively, may bealigned randomly, or may be aligned so that a free end points toward aperipheral edge, or a center, of a barrier article.

In one embodiment, barrier structures may be arrayed randomly in thebarrier layer. In one embodiment, barrier structures may be arrayed in apattern in a barrier layer. Suitable patterns may include offset rows,substantially uniform rows, substantially uniformly arrayed clusters ofbarrier structures, and the like. In one embodiment, rows of clusters ofbarrier structures may be arranged on a surface of the base layer. Ifdiffering types of barrier structures are used, each type may bearranged in a pattern independent of each other type, or may be arrangedwith reference to one or more other type of barrier structure.

Barrier structures may be formed from materials that may include metal,polymers, glass, ceramic, cermet, natural materials such as stone andwood, and composite materials, and the like, and combinations of two ormore of the foregoing. Suitable polymers, metals, glasses, ceramics,cermets, and the like may be substantially the same as those listedhereinabove as suitable for use in forming a base layer. In oneembodiment, the barrier structure and the base layer may includesubstantially the same material. In one embodiment, the barrierstructure and the base layer may include substantially differentmaterials.

A metal barrier structure may be formed of spring steel, and may beconfigured as a caltrop, or as having one or more projections and asubstantially wide base. In such an embodiment, a thermoplastic baselayer may be used in combination with a dual adhesive type adhesivelayer. The thermoplastic base layer may be a flexible, high-temperaturepolyolefin based polymer having a reinforcement of glass fiber weave.The adhesive layer may include a light duty pressure sensitive adhesivedisposed in discontinuous amounts throughout a substantially continuouslayer of moisture cured structural adhesive. During manufacture,extended sharp ends of the barrier structure may be forced through amolten base layer, and the glass fiber reinforcement so that the barrierlayer base is on an opposite side of the base layer from the projectionfree ends. The barrier layer may be cooled, and may harden. The adhesivelayer may be then applied over the base layer surface having the barrierlayer base. Optionally, a release liner may be placed over the adhesivelayer, over the barrier layer, or both.

In one embodiment, a base layer may have a layer of structural adhesivecoated onto a side thereof, and a plurality of barrier structuresadhered to the base layer using the adhesive coating following a curingstep. A second adhesive layer may be applied to an opposite side of thebase layer. Optionally, an additional device, such as a device describedhereinbelow, may be embedded between, for example, the second layer andthe base layer during manufacture. Optionally, a reinforcing layer suchas a metal mesh, which may be initially distinct from the base layer,may be embedded in the adhesive layer during manufacture.

In one embodiment, a barrier structure may be formed from a frangiblematerial, such as glass, ceramic, cermet, brittle metal, and the like,or combinations of two or more thereof. Naturally, frangible barrierstructures may be included in barrier articles that may be disposableand/or replaceable after use. Such frangible barrier structures may, ofcourse, be used in combination with more robust barrier structures, ifdesired. Frangible barrier structures may be uniformly distributedthroughout a barrier layer, or may be randomly distributed throughout.In one embodiment, a frangible barrier structure may be disposed below alevel of other non-frangible barrier structures, which may preventunwanted access or tampering with the frangible barrier structures priorto their intended use.

Suitable frangible barrier structures may be hollow, and may be filledwith one or more predetermined compositions. Such filled frangiblebarrier structures are referred to as ampoules, and such predeterminedmaterials that may fill the ampoules are referred to as ampoule loads.In one embodiment, an ampoule may be pointed or sharp to facilitatepuncturing, for example, clothing, skin, and/or protective gear. In oneembodiment, an ampoule may be dull or rounded, and may be configured tobreak easily in response to tampering or pressure beyond that associatedwith installation or application.

As noted above, an ampoule may be loaded with one or more compositions.Amounts and concentrations of an ampoule load may be constrained by avolume of the interior of an ampoule, and desired effect of the ampouleload. In one embodiment, an ampoule load amount may be less than about0.1 gram, in a range of from about 0.1 gram to about 0.5 grams, fromabout 0.5 grams to about 1 gram, or more than about 1 gram.

Suitable ampoule loads may include liquid, solids, waxy solids, powderedsolids, gases, and combinations thereof. Suitable solids may includepowders of crystallized liquids, and powdered carrier materialsimpregnated or including a liquid. Suitable liquids may includesolutions, slurries, and the like of solid materials. Examples ofsuitable composition materials for use as ampoule loads are disclosedhereinbelow. Selection of composition materials may be made withreference to a desired effect of the material, the end use, useconditions, availability of materials, intended length of service, andthe like, and combinations of two or more thereof.

Suitable ampoule load compositions may include one or more adhesive;incapacitating agent; lachrymator; vesicant; nerve agent; pulmonaryagent; toxin; malodorant; derivative or analog of any of the foregoing;or the like, and combinations of two or more thereof. Alternatively, aplurality of ampoules may include, separately, precursors to the aboveload compositions, which, when ampoules are broken and the precursorcontents are mixed may form an ampoule load composition as disclosedabove. Additional compositions for the load may include one or more of amarking agent, an additive, or the like.

Suitable adhesives may include one or more of the adhesives describedhereinabove with reference to the adhesive layer. In one embodiment, theadhesive may include a quick setting cyanoacrylate adhesive, such ascommercially available methyl-2-cyanoacrylate or 2-octyl cyanoacrylate.

Suitable incapacitating agents may include nervous system affecters,vomiting agents, choking agents, hallucinogens, sedatives, narcotics,depressants, and the like, and combinations of two or more thereof. Inone embodiment, an incapacitating agent may include 3-quinuclidinylbenzilate (QNB, BZ), which may be an anticholinergic agent that affectsboth the peripheral and central nervous systems (CNS). Alternativenervous system affecters may include commercially available over thecounter (OTC) or prescription pharmaceutical compositions. In oneembodiment, an incapacitating agent may include curare, or a curareanalog or derivative.

Suitable lacrymators, or irritants, may include compositions that causetearing and/or inflammation of the mucous membrane proximate to theeyes. In one embodiment, a lacrymator may include one or more ofo-chlorobenzylmalonitrile, chloromethyl chloroformate, stannic chloride,sym-dichloromethyl ether, benzyl bromide, xylyl bromide, methylchlorosulphonate, ethyl iodoacetate, bromacetone, bromomethyl-ethylketone, acrolein (2-propanal), capsaicin and derivatives, or the like.

A suitable vesicant or blister agent may cause blisters when contactedto skin. In addition to causing blisters, a vesicant may damagemembranes. Tissues that may be vulnerable to vesicant action may includeone or more of eyes and airways by topical contact, or thegastrointestinal tract and/or bone marrow after absorption. A suitablevesicant may include one or more of sulfur mustard, nitrogen mustard, oran arsenical, such as Lewisite, and combinations of two or more thereof.Suitable sulfur mustard may include one or more of 2-chloroethylchloromethyl sulfide, bis(2-chloroethyl) sulfide or dichloroethyldisulfide, bis(2-chloroethylthio) methane, 1,2-bis(2-chloroethylthio)ethane, 1,3-bis(2-chloroethylthio)-n-propane,1,4-bis(2-chloroethylthio)-n-butane,1,5-bis(2-chloroethylthio)-n-pentane, bis(2-chloroethylthiomethyl)ether, bis(2-chloroethyl thioethyl) ether, combinations of two or morethereof. Suitable nitrogen mustard may include one or more ofbis(2-chloroethyl) ethylamine, bis(2-chloroethyl) methylamine, ortris(2-chloroethyl) amine, or combinations of two or more thereof.Suitable Lewisites may include one or more of2-chlorovinyldichloroarsine, bis(2-chlorovinyl) chloroarsine,tris(2-chlorovinyl) arsine, or combinations of two or more thereof.

A vesicant, once released from an ampoule and contacted to skin, maycross the skin or mucous membrane barrier. A vesicant may attach tocellular or tissue components where the vesicant later may cause damage.Effects from a suitable vesicant may appear in less than about 5minutes, in a range of from about 5 minutes to 1 hour, from about 1 hourto about 2 hours, from about 2 hours to about 24 hours after contact.

Suitable nerve agents may include cholinesterase inhibitors. In oneembodiment, a cholinesterase inhibitor may include one or more ofo-alkyl (Me, Et, n-Pr or i-Pr)-phosphonofluoridates, such as o-isopropylmethylphosphonofluoridate (sarin) or o-pinacolylmethylphosphonofluoridate (soman); o-alkyl N,N-dialkyl (Me, Et, n-Pr ori-Pr) phosphoramidocyanidates, such as o-ethyl N,N-dimethylphosphoramidocyanidate (tabun); or o-alkyl S-2-dialkyl (Me, Et, n-Pr ori-Pr)-aminoethyl alkyl (Me, Et, n-Pr or i-Pr) phosphonothiolates andcorresponding alkylated or protonated salts, such as o-ethylS-2-diisopropylaminoethyl methyl phosphonothiolate (VX); andcombinations thereof.

Suitable pulmonary agents may include one or both of phosgene (carbonylchloride) and perfluororoisobutylene. After inhalation, a pulmonaryagent may breakdown the alveolar-capillary membrane, which may allowplasma to leak into the alveoli. Suitable toxins may include one or moreof palytoxin, ricin, saxitoxin, or botulinum toxin, or combinations oftwo or more thereof.

Suitable blood agents may include forms of cyamide, such as salts,analogs and derivatives. A suitable solid salt of cyamide may includesodium, potassium, and/or calcium. A suitable volatile liquid form ofcyamide may include hydrogen cyamide and/or cyanogen chloride. Theaddition of an acid, such as sulfuric acid, may be co-packaged inseparate ampoules so that crushing a plurality of ampoules may releaseboth cyamide and the acid. Cyamide may inhibit the cellular enzymecytochrome oxidase to inhibit oxygen metabolism and energy generation bythe cell. Most signs and symptoms are of central nervous system originand after inhalation of a large amount include a brief period ofhyperpnea, seizures, a decrease in breathing rate until apnea occurs,and at sufficiently large dosages cardiac arrhythmia. A slowerabsorption may lead to effects including vertigo, nausea, and a feelingof weakness.

In one embodiment, an ampoule load may include a malodorant composition.Suitable malodorant compositions may include a malodorant compound. Asuitable malodorant composition may contact and stimulate the olfactoryand/or trigeminal nerves of proximate persons to the release. Anexpected response may be characterized by a strong desire to avoid thesubstance and may be accompanied by immediate nausea and gagging.Persons exposed to the malodorant may be averse thereto and may wish toexit from an area in which a malodorant has been dispersed or released.

In one embodiment, a malodorant compound may include one or moresulfur-based compounds, nitrogen-based compounds, halogen-basedcompounds, both nitrogen- and sulfur-based compounds, or metal-basedcompounds. An organic component of a malodorant compound may include oneor more linear, non-linear, aromatic, and/or cyclic arrangement ofcarbon atoms, and may contain saturated and/or unsaturated carbonbonding.

A suitable malodorant composition may include one or more indolesselected from 2-methyl indole, 3-methyl indole, 4-methyl indole,5-methyl indole, 6-methyl indole, and 1-Butyl indole. Additionalsuitable odorants may include musk, hydrogen sulfide, aliphatic diaminessuch as putrescine (tetramethylene diamine) or cadaverine(pentamethylene diamine), dicrotyl sulfide, butyl mercaptan, and thelike.

Suitable malodorant compounds may include mercaptans, thiols, sulfides,disulfides, sulfoxides, sulfones, sulfonic acids, sulfinic acids,thio-acids, dithio-acids, thiolo-acids, thiono-acids, sulfonyl halides,thiazoles, sulfur amines, sulfides, amides, organic derivatives, and thelike, including mixtures of any two or more of the foregoing. Suitablenon-limiting examples of such compounds include methyl mercaptans, ethylmercaptans, propyl mercaptans, butyl mercaptans, amyl mercaptans, phenylmercaptans, benzyl mercaptans, 2-mercaptoethanol, 1,2-ethanedithiol,3-methyl-1-butanethiol, ethylcyclohexydithiol, d-limonene dimercaptan,vinyl cyclohexene-derived dimercaptan, perchloromethyl mercaptan, methylsulfide, ethyl sulfide, propyl sulfide, isopropyl sulfide, ethyl methylsulfide, dimethyl sulfide, dimethyl disulfide, diethyl sulfide,di-n-propyl disulfide, butyl disulfide, bibutyl sulfide, trimethylenesulfide, ethylene sulfide, propylene sulfide, allyl sulfide,mercaptoethyl sulfide, cyclopropyl phenyl sulfide, dimethyl trisulfide,dimethyl sulfoxide, propyl allyl sulfoxide, 3-chloropropyl n-octylsulfoxide, allyl n-octyl sulfoxide, 2-methallyl n-octyl sulfoxide,methanesulfonic acid, methanesulfonyl chloride, ethanesulfonyl chloride,propanesulfonyl chloride, benzothiazole, 2-mercapto benzothiazole,N-isopropyl-2-benzothiazole sulfenamide,N,N-diisopropyl-2-benzothiazolesulfenamide, N-tert-butyl-2-benzthizolesulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, N,N-dicyclohexylbenzothiazole sulfenamide, and other like malodorous organic sulfurcompounds, including mixtures of any two or more of the foregoing.

In one embodiment, suitable organic sulfur compounds may includealiphatic mercaptans, and analogs, derivative, and salts thereof. In oneembodiment, the aliphatic component of the mercaptan includes from about3 to about 12 carbon atoms per molecule. Examples of such compoundsinclude methyl mercaptans, ethyl mercaptans, propyl mercaptans,isopropyl mercaptans, n-butyl mercaptans, isobutyl mercaptans, s-butylmercaptans, t-butyl mercaptans, n-amyl mercaptans, s-amyl mercaptans,isoamyl mercaptans, t-amyl mercaptans, n-hexyl mercaptans, n-heptylmercaptans, n-octyl mercaptans, s-octyl mercaptans, n-nonyl mercaptans,t-nonyl mercaptans, n-decyl mercaptans, undecyl mercaptans, n-dodecylmercaptans, t-dodecyl mercaptans, triisobutyl mercaptans, and the like,including mixtures of any two or more of the foregoing.

The concentration of the malodorant composition in embodiments of theinvention may differ depending on such factors as, for example, theparticular malodorant compound employed, structural considerations ofthe barrier layer, other compositions present, and on the intendedapplication for the malodorant composition and the article.

In one embodiment, the malodorant may include an organic sulfur compoundpresent at a concentration in the range of from about 1 weight percentto about 100 weight percent, from about 1 weight percent to about 10weight percent, from about 10 weight percent to about 50 weight percent,or from about 50 weight percent to about 75 weight percent. Here andthroughout the specification and claims, the range limits may becombined and interchanged.

In addition to the malodorant compound, the malodorant composition mayinclude one or more additives. Suitable additives may include one ormore odor intensifier, diluent, oil, flow modifier, tackifier,thickener, heat stabilizer, preservative (e.g., EDTA), effervescent,foaming agent, wetting agent, anti-foaming agents, anti-static agents,or marking agent. In one embodiment, an odor intensifier may be skatole.Skatole is an indole and may be a component of fecal matter. The term“skatole” includes the compound 3-methylindole.

Suitable diluents may include aqueous solutions, organic solvents, andoils. Suitable organic solvents may include natural and syntheticesters, ethers, ketones, nitriles, hydrocarbons, and mixtures of any twoor more of the foregoing.

Suitable oils may include natural oils and mineral oils. Suitablenatural oils may include almond oil, castor oil, corn oil, cottonseedoil, hemp oil, linseed oil, olive oil, peanut oil, rapeseed oil, sesameoil, safflower oil, tung oil, and the like, and combinations of two ormore thereof. Suitable mineral oils may include synthetic oils such ashomo- and inter-polymers of C2-C12 olefins, carboxylic acid esters ofboth monoalcohols and polyols, polyethers, silicones, polyglycols,silicates, alkylated aromatics, carbonates, thiocarbonates,orthoformates, phosphates and phosphites, borates and halogenatedhydrocarbons. Additional suitable synthetic oils may include the estersof dicarboxylic acids (e.g., phthalic acid, succinic acid, maleic acid,azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid,linoleic acid dimer) with a variety of alcohols (e.g., butyl alcohol,hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, and ethyleneglycol). Suitable esters may include dibutyl adipate, di(2-ethylhexyl)adipic, didodecyl adipate, di(tridecyl) adipate, di(2-ethylhexyl)sebacate, dilauryl sebacate, di-n-hexyl fumarate, dioctyl sebacate,diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecylphthalate, di(eicosyl) sebacate, and 2-ethylhexyl diester of linoleicacid dimer.

Suitable silicon-based oils may include polyalkyl-, polyaryl-,polyalkoxy-, and polyaryloxy-siloxane oils and silicate oils, e.g.,tetraethyl silicate, tetra isopropyl silicate, tetra(2-ethylhexyl)silicate, tetra(p-tert-butylphenyl) silicate, poly(methyl) siloxanes,and poly(methylphenyl) siloxanes). Other suitable synthetic oils mayinclude liquid esters of phosphorus-containing acids (e.g., tricresylphosphate, trioctyl phosphate, triphenyl phosphite, and diethyl ester ofdecane phosphonic acid.

In one embodiment, the ampoule load may include additional materials.These additional materials may include one or more of preservatives,such as ethylene diamine tetraacetic acid (EDTA), viscosity modifiers,foaming agents or anti-foaming agents, anti-static agents,effervescents, and the like, including mixtures of any two or more ofthe foregoing. An effervescent may cause an evolution of bubbles of gasfrom a liquid as a result of a chemical reaction.

A suitable ampoule load may include a marking agent. Suitable markingagents may include a non-washable, semi-permanent to permanent marker ofclothes, uniforms, equipment and/or skin. In one embodiment, a markingagent includes dense pigmentation to allow for improved visibility. Toincrease contrast and visibility, the marking agent may be a brightcolor, such as yellow, orange, white, and the like. In one embodiment, amarking agent may be florescent, iridescent, and/or luminescent. In oneembodiment, a marking agent may include a material that fluoresces inresponse to exposure to ultraviolet light. In one embodiment, themarking agent may include one or more materials that are not visiblemarking materials, but may be detectable by other means, such asmagnetic particles, coded crystalline structures, miniature bar codes,pre-selected protein sequences, and the like.

In one embodiment, an ampoule may be pressurized, for example, withcarbon dioxide or nitrogen gas. Alternatively, an ampoule may include amaterial that foams and/or effervesces in contact with air to create apropulsive force that may, for example, project or spread an ampouleload. In another embodiment, an ampoule may be rugged and resistant tofracture in a first direction, but fragile and easy to fracture inresponse to force applied in a second, different direction.

A barrier article 200 comprising an embodiment of the invention is shownin FIG. 2. The barrier article 200 may include a base layer 210, anadhesive layer 220 disposed on a first surface of the base layer 210,and a barrier layer 230 disposed on a second surface of the base layer210, opposite the adhesive layer 220. The barrier layer 230 may includea barrier structure 232 that is one of a plurality of like barrierstructures, or dissimilar barrier structures 234. Each barrier structure232 may have a first portion proximate to the base layer 210, and adistal portion spaced from the base layer 210. A release liner 240 maybe releasably secured to the barrier layer 230 and to the second surfaceof the base layer 210. The release liner 240 has a thickness thatextends from the base layer second surface outward beyond the distalportion of the barrier structure 232.

In one embodiment, a release liner may include a non-compressible or arelatively low compressible material. Suitable release liners may beformed from, for example, closed cell foamed polymers. Suitable polymersmay include those polymers listed as suitable for use in a base layer.In one embodiment, a release liner may be multi-layered, and one of thesub-layers may include, for example, a flexible metal layer ormetallized polymer layer. Suitable expansion agents for use in formingfoamed layers may include thermoplastic hollow spheres, such as EXPANCEL551DU, which is commercially available from Expancel, Inc. (Duluth,Ga.). Other suitable expansion agents may include one or more ofdiazoaminobenzene; azobis (isobutyronitrile); dinitroso pentamethylenetetramine; N,N′-dinitroso-N,N′-dimethylterephthalamide;azodicarbonamide; sulfonyl hydrazides; benzene sulfonyl hydrazide;toluene sulfonyl hydrazide; oxybis(benzene sulfonyl hydrazide); sulfonylcarbazides; azodicarboxylic acid esters; or azodicarboxylic acid salts;and the like.

The release liner 140 may be formed in place on and around the barrierlayer 130. Barrier structures 232, 234 of the barrier layer 130 may betherefore releasably encased in the release liner 140.

During use, the release liner 140 blocks access to the barrier layer130, that is, pressure may be applied to an outer surface of the releaseliner 140 and the distal portion of a barrier structure 232 does notpuncture either the release liner or, for example, a hand that isapplying the pressure. Additionally, the frangible barrier structure 234in the barrier layer 130 may be protected from breakage, particularlyduring manufacture, storage, transport, and installation by the releaseliner 140. The barrier article 200 may be adhesively secured to asurface of a substrate 250, such as concrete. One placed in adhesivecontact with the substrate, the barrier article 200 may have the releaseliner 140 removed and/or discarded, as shown in FIG. 2 with a portion ofthe release liner 140 removed or peeled back. Removal of the releaseliner 140 exposes the barrier layer 130, which may provide a barrierfunction, or a deterrent function.

With reference to FIG. 3, a barrier article 300 according to embodimentsof the invention is shown. The barrier article 300 may include adual-adhesive type adhesive layer 310, a metal-mesh or fiber-meshreinforcing layer 320, a reinforced polymeric base layer 330, and abarrier layer 340. As shown, a first barrier structure 342 may be formedof resilient metal and extends through the base layer 330 to pointedfree ends 344, 346. A second barrier structure 350 may be formed ofcarbon-carbon composite and may be adhered to an exposed surface 352 ofthe base layer 330 by a secured portion 354, and may have a shaft 355that may extend from the surface 352 at an angle of about 45 degrees toa sharp free end 356 having a barb structure 358 thereon. A thirdbarrier structure 360 may be formed from frangible glass and may have aninterior surface that defines a volume 362 of about 0.5 milliliters. Aload 364 in the volume 362 may include an ampoule load, as describedherein. In the embodiment illustrated in FIG. 3, the ampoule load mayinclude a marking agent, an incapacitating agent, an effervescent, afoaming agent, a carrier liquid, and a malodorant. The marking agent mayinclude a permanently-staining visual-fluorescent Day-Glo type dye. Themalodorant may include a mercaptan. The incapacitating agent may includecapsaicin. The carrier liquid may include a short chain alcohol. Thefoaming agent may include a surfactant. The effervescent may include,for example, sodium bicarbonate, citric acid and tartaric acid, whereinthe acid and base may react to form bubbles of carbon dioxide, water anda salt.

Barrier articles comprising embodiments of the invention may beconfigured to have widths and lengths tailored, or tailorable, toparticular applications or end uses. Suitable widths may be less than 1centimeter, in a range of from about 1 centimeter to about 25centimeters, from about 25 centimeters to about 75 centimeters, fromabout 75 centimeters to about 150 centimeters, from about 150centimeters to about 250 centimeters, from about 250 centimeters toabout 500 centimeters, from about 500 centimeters to about 1 meter, fromabout 1 meter to about 2.5 meters, or greater than about 2.5 meters.Suitable lengths may be less than 25 centimeters, in a range of fromabout 25 centimeter to about 75 centimeters, from about 75 centimetersto about 175 centimeters, from about 175 centimeters to about 350centimeters, from about 350 centimeters to about 500 centimeters, fromabout 500 centimeters to about 1 meter, from about 1 meter to about 5meters, from about 5 meters to about 10 meters, from about 10 meters toabout 25 meters, or greater than about 25 meters. In one embodiment, abarrier article is a relatively long and narrow tape, which optionallymay be in a roll prior to use. In one embodiment, a barrier article maybe configured as squares that are about 300 centimeters to a side, andwhich may be used side-by-side to cover an area of a substrate.

In one embodiment, strips of a barrier article may be sized and shapedto wrap around poles, such as light poles, telephone poles, gutters, andthe like. Other shapes may also be suitable, such shapes may includeirregular or customized shapes, circles and ovals, triangles, zig-zags,sinusoids, rings, and/or polygons. In one embodiment, a barrier articlemay be configure so that rather than the thickness laying in a plane,the barrier article defines a loop has a barrier layer facing inwardstoward an axis, and an adhesive layer facing outwards away from theaxis. In such an embodiment, an interior of, for example, a window wellmay be lined with the barrier article. Alternatively, the barrier layermay face away from the axis, and the adhesive layer may face toward theaxis. In such an embodiment, an exterior of, for example, a drum may bewrapped with a barrier article.

With reference to FIG. 4, a multi-component barrier article 400comprising an embodiment of the invention is shown. The barrier article400 may include a first component 402, which may have a first adhesivelayer 404, a first base layer 406, and a first barrier layer 408; and asecond component 410, which may have a second adhesive layer 412, asecond base layer 414, and a second barrier layer 416. A conductiveelement system 420 communicates with a monitor and alarm unit 422. Theconductive element system 420 may include a first conductive fiber 428embedded in the matrix of the first component base layer 404, and asecond conductive fiber 430 embedded in the matrix of the secondcomponent base layer 414. A connector 440 communicates the firstconductive fiber 428 with the second conductive fiber 430.

In one embodiment, a conductive element has a length that extends beyonda peripheral edge of a barrier article component to a connector. Duringinstallation, the connector can be connected to another connector toextend the conductive element, and excess length may be tucked under,and sealed under, the adhesive layer as the adhesive layer is secured toa substrate. In one embodiment, a conductive element may extend along aperipheral edge of a barrier article, or may cross back and forth alonga length of the barrier article. Other arrangements of a conductiveelement may be selected with reference to an end use or application.

During use, tampering with the barrier article 400 may cause the monitorand alarm system 422 to detect the tampering via the conductive fibers428, 430 and respond in a predetermined manner to report the tamperingevent.

Additional devices may be included in embodiments according to theinvention, and may communicate directly or indirectly with receiversand/or monitors. Suitable devices may include one or more conductiveelements, such as conductive fibers and conductive sheets. Suitableconductive elements may function as one or more of vibration sensors,continuity sensors, radio frequency identification devices (RFID),tamper sensors, flexion sensors, temperature sensors, and the like, andconnectors for the foregoing. Strips of a barrier article may be appliedto a substrate surface, and one or more of the conductive elementsembedded therein may be connected from strip to strip using a connectorto form a continuous length of conductive elements. Such a continuouslength of conductive elements may be linear, may form a completecircuit, or may be in a web or net-like arrangement.

Conductive elements may include structures that extends throughout abase layer, an adhesive layer, and/or a barrier layer, and which conductenergy of a predetermined type. In one embodiment, the energy may belight from, for example, a light emitting diode (LED) or may be coherentlight energy from a laser source. In one embodiment, the light energycan have a wavelength of less than about 850 nanometers (nm), in a rangeof from about 850 nm to about 1550 nm, or greater than about 1550 nm.Commercially available LED light sources may generate light having awavelength closer to about 850 nm, while commercially available laserlight sources typically generate light with a frequency closer to about1550 nm. But, vertical cavity surface emitting lasers (VCSEL) typicallygenerate light with a frequency closer to about 850 nm and also may besuited for use in the present embodiment.

In other embodiments, the energy may be electrical, heat, magnetic,other energy along the electromagnetic spectrum, or the like. The typeof energy conducted can constrain the type of materials useful forforming the pathway. For example, energy may be light and the pathwaymay be an optical fiber or a bundle of like or dissimilar opticalfibers. Suitable fibers may include glass fibers, such as thosecommercially available from Corning Cable Systems LLC (Hickory, N.C.).In one embodiment, optical fiber bundles may include polymeric fibers,or may be a combination of glass fibers and polymeric fibers. Suitablepolymeric fibers include those with a methyl methacrylate core withfluorinated polymer cladding such as RAYTELA brand fibers, which arecommercially available from Toray Industries (America), Inc.

In one embodiment, an optical fiber or optical fiber bundle may define aridged cable. That is, an exterior surface of a fiber optic cable mayhave ridges to facilitate gripping in an embedded layer or a receivingstructure. The embedded layer or a receiving structure may be single useor reusable. For reusable applications, the embedded layer or areceiving structure may define an elongate aperture through whichsubsequent replacement fiber optic bundles or cables may be inserted.Thus, for ridged cable embodiments, ridges may engage an inner surfacethat defines the elongate aperture and mechanically secure the cable inplace. In one embodiment, the ridges may be angled and allow movement ofthe cable relative to the aperture-defining inner surface in onedirection only. In one embodiment, the optical fibers have attachmentson an end of each fiber, or on the end of the cable if bundled. Theattachments may prevent a fiber or cable from being re-inserted into theembedded layer or a receiving structure once the fiber or cable has beenremoved from the embedded layer or a receiving structure.

As a further illustration of a suitable alternative conductive elementin accordance with embodiments of the invention, a conductive elementmay be electrically conductive, or semi-conductive if the energy iselectrical energy. In one embodiment, a conductive element may be aprinted layer of electrically conductive ink, a layer of electricallyconductive polymer, a layer of polymer doped or filled with electricallyconductive filler material (e.g., nickel flake, carbon powder, ormetallic fibers), a metal foil, or the like, supported on a surface of abase layer. Suitable electrically conductive inks may be commerciallyavailable from DuPont Electronic Materials, Inc. (Wilmington, Del.). Anelectrically conductive pathway comprising metal may be produced by, forexample, chemical vapor deposition (CVD), sputtering coating, and/orprinting with the metallic ink. Suitable metals for use in anelectrically conductive pathway may include one or more of includetitanium, silver, gold, aluminum, copper, iron, and alloys of thesemetals.

With reference to the monitor and alarm unit, in one embodiment amonitor and alarm unit may communicate directly to conductive element,but in another embodiment, the monitor and alarm unit may communicatewith a signaling device, such as an RFID device, which is in directcommunication with a conductive element. Accordingly, tampering with aconductive element (by exerting, for example, pressure, temperature,vibration, flexion, and the like, or by breaking continuity) may resultin a signal being generated and sent to a monitor and alarm unit, eitherdirectly, or indirectly via, for example, a wireless device.Alternatively, in one embodiment, a conductive element may be passive,and may respond to a query by a monitor and alarm unit by not generatinga signal, from which a monitor and alarm unit may infer tampering hasoccurred.

In one embodiment, a monitor and alarm unit may include a receiver for asignal generated by a radio frequency identification device (RFID)embedded in a base layer, adhesive layer, or barrier layer. In oneembodiment, the RFID may be capable of interacting passively, and inother embodiments the RFID may be actively interactive with an RFIDsensor located remote from the RFID, which may be in communication withthe monitor and alarm unit. In addition, the RFID may include one ormany optional components. Such optional components include an antenna, amemory chip, a power source, a receiver, a transmitter, a transponder, alight-to-electricity converter, integrated circuit. In one embodiment,other commercially available wireless communication devices may be usedto communicate with an associated sensor, either actively or passively.Such alternative wireless communication devices include Bluetoothenabled devices, as well as other devices that utilize non-radiofrequency electro-magnetic energy.

With reference to an antenna, various configurations may be possible forthe antenna. In one embodiment, an antenna may include a plurality ofdistinct, separate antennas. One antenna may be provided for receiverfunctions and another antenna may be provided for transmitter functions.In one embodiment, a single antenna may be shared and functions as boththe receiver and transmitter, or transponder. In one embodiment, anantenna may be defined by a conductive epoxy structure screen printed orflexographically printed onto a flexible insert. An antenna may beconductively bonded to the RFID via bonding pads. In an embodiment wherea single antenna may be employed, that single antenna can include afolded dipole antenna defining a continuous conductive path, or loop, ofmicrostrip. Alternatively, an antenna can be constructed as a continuousloop antenna.

For RFIDs that actively interact, they may include a power source. Inone embodiment, the power source may be a battery. If the power sourceis a battery, the battery may take any suitable form. Factors that canbe considered in pre-selecting the battery type include the weight,size, flexibility, power output, and life requirements for a particularapplication. In one embodiment, a battery may be a thin profilebutton-type cell forming a small, thin energy cell commonly utilized inwatches and small electronic devices requiring a thin profile. Aconventional button-type cell has a pair of electrodes, an anode formedby one face and a cathode formed by an opposite face. In one embodiment,the battery includes, in series, connected pairs of button type cells.In one embodiment, the battery is a flexible polymeric battery.

In one embodiment, the RFID transmits and receives radio frequencycommunications to and from a sensor communicating with the RFID. TheRFID sensor can include an antenna and dedicated transmitting andreceiving circuitry, similar to that implemented on the RFID. Oneexample of an RFID sensor implemented in combination with a transponderunit may be disclosed in U.S. Pat. No. 4,857,893, which is herebyincorporated by reference to the extent it discloses RFID sensors. TheRFID can include one or more receivers. If more than one receiver isused, one can be a low power receiver for detecting a wake up signalfrom an RFID sensor, and another can be a high power receiver forreceiving commands from an RFID sensor. The antenna may be constructedand arranged to form a folded dipole antenna that may be thedual-function continuous conductive element or a loop. Terminal ends ofthe antenna form conductive leads that electrically interconnect withthe RFID.

In one embodiment, a monitor and alarm unit may be a flip chip having amemory and may be electrically connectable using commercially availablechip attachment methods. For example, the monitor and alarm unit may beelectrically attached using a conductive adhesive, such as a polymericconductive adhesive or an anisotropic conductive adhesive, which may bedispensed using, for example, a needle and syringe.

In one embodiment, a graphic layer may be overlayed onto a base layersuch that an image or text may be visible through a barrier layer. Sucha graphic layer image may include, for example, a warning statement.Suitable graphic layers may be formed via printing, coextrusion, and thelike. In one embodiment, a graphic layer may be applied to a base layerduring formation of the base layer, and prior to adding a barrier layer.In one embodiment, a graphic layer may include a dry paint layer thatmay be applied in liquid form to an otherwise complete barrier article,particularly prior to the addition of a release liner over a barrierlayer. In one embodiment, a graphic layer may include luminescent ink,or fluorescent ink, or both.

The processes and embodiments described herein may be examples ofstructures, systems, compositions, and methods having elementscorresponding to the elements of the invention recited in the claims.This written description may enable those of ordinary skill in the artto make and use embodiments having alternative elements that likewisecorrespond to the elements of the invention recited in the claims. Theintended scope of the claimed invention thus includes other structures,systems, compositions, and methods that do not differ from the literallanguage of the claims, and further includes other structures, systems,compositions, and methods with insubstantial differences from theliteral language of the claims.

1. A barrier article, comprising: a base layer; an adhesive layer supported on a first surface of the support layer; and a barrier layer supported on a second surface of the support layer, opposite the adhesive layer.
 2. The article as defined in claim 1, wherein the base layer comprises one or more of polymer, metal, ceramic, or glass.
 3. The article as defined in claim 2, wherein the polymer comprises one or more of polyacrylamide, polyacrylate, polyamide, polycarbonate, epoxy, polyester, polyether, ionomer, polyimide, polyolefin, polystyrene, polyurethane, polyvinyl, silicone, polysiloxane, or norbornene polymer.
 4. The article as defined in claim 1, wherein the base layer comprises reinforcement comprising one or more of metal, glass or polymer.
 5. The article as defined in claim 1, wherein the adhesive layer comprises one or more of a pressure sensitive adhesive, a structural adhesive, a hot melt adhesive, or a curable adhesive.
 6. The article as defined in claim 5, wherein the adhesive layer comprises one or more of acrylate, amide, acrylonitrile, carbonate, cyanate ester, cyanurate, ethylene-vinyl acetate, epoxy, fluoroplastic, ionomer, methyl methacrylate, non-ethylenic olefin polymer (linear or branched), nylon, olefin, polyester, styrene, styrene-maleic anhydride, sulfone, styrene-acrylonitrile, or urethane.
 7. The article as defined in claim 1, wherein the adhesive layer comprises reinforcement.
 8. The article as defined in claim 1, wherein the barrier layer comprises one or more of polymer, metal, ceramic, or glass.
 9. The article as defined in claim 1, wherein the barrier layer comprises a barrier structure that is configured to cut or puncture contacting skin, cloth, or both.
 10. The article as defined in claim 1, wherein the barrier layer comprises a barrier structure that is configured as a pin, a needle, a blade, a hook, a barb, or a combination of two or more thereof.
 11. The article as defined in claim 1, wherein the barrier layer comprises a frangible barrier structure having an inner surface that defines a volume, and the volume is filled with an ampoule load.
 12. The article as defined in claim 11, wherein the ampoule load comprises one or more of an adhesive; incapacitating agent; lacrymator; vesicant; nerve agent; pulmonary agent; toxin; malodorant; a derivative, precursor, or analog of any of the foregoing; visual marking agent; or, non-visual marking agent.
 13. The article as defined in claim 12, wherein the malodorant comprises one or more of 2-methyl indole, 3-methyl indole, 4-methyl indole, 5-methyl indole, 6-methyl indole, and 1-butyl indole, musk, hydrogen sulfide, aliphatic diamines, tetramethylene diamine, pentamethylene diamine, dicrotyl sulfide, butyl mercaptan, methyl mercaptan, ethyl mercaptan, propyl mercaptan, amyl mercaptan, phenyl mercaptan, benzyl mercaptan, 2-mercaptoethanol, 1,2-ethanedithiol, 3-methyl-1-butanethiol, ethylcyclohexyldithiol, d-limonene dimercaptan, vinyl cyclohexene-derived dimercaptan, perchloromethyl mercaptan, methyl sulfide, ethyl sulfide, propyl sulfide, isopropyl sulfide, ethyl methyl sulfide, dimethyl sulfide, dimethyl disulfide, diethyl sulfide, di-n-propyl disulfide, butyl disulfide, bibutyl sulfide, trimethylene sulfide, ethylene sulfide, propylene sulfide, allyl sulfide, mercaptoethyl sulfide, cyclopropyl phenyl sulfide, dimethyl trisulfide, dimethyl sulfoxide, propyl allyl sulfoxide, 3-chloropropyl n-octyl sulfoxide, allyl n-octyl sulfoxide, 2-methallyl n-octyl sulfoxide, methanesulfonic acid, methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, benzothiazole, 2-mercapto benzothiazole, N-isopropyl-2-benzothiazole sulfenamide, N,N-diisopropyl-2-benzothiazolesulfenamide, N-tert-butyl-2-benzthizole sulfenamide, N-cyclohexyl-2-benzothiazole, sulfenamide, or N,N-dicyclohexyl benzothiazole sulfenamide.
 14. The article as defined in claim 12, wherein the malodorant comprises one or more of mercaptan, thiol, sulfide, disulfide, sulfoxide, sulfone, sulfonic acid, sulfinic acid, thio-acid, dithio-acid, thiolo-acid, thiono-acid, sulfonyl halide, thiazole, sulfur amine, sulfide, amide, or organic derivatives of the foregoing.
 15. The article as defined in claim 12, wherein the ampoule load comprises one or more of a preservative, viscosity modifier, foaming agent, anti-foaming agent, anti-static agent; effervescent, or a pressurized gas.
 16. The article as defined in claim 12, wherein the non-visual marking agent comprises one or more of magnetic particles, laser etched particles, holographic crystals.
 17. The article as defined in claim 1, further comprising an RFID supported by or embedded in, or supported by, one or both of the support layer or the adhesive layer.
 18. The article as defined in claim 1, further comprising a conductive element supported by or embedded in one or more of the support layer, the adhesive layer, or the barrier layer.
 19. The article as defined in claim 1, further comprising a release liner that is releasably secured to a surface of the adhesive layer opposite the base layer.
 20. A barrier article, comprising: means for adhering the barrier article to a substrate; and means for discouraging a person to contact with an exposed surface of the barrier article.
 21. A method, comprising: securing a plurality of barrier structures to a base layer, each of the barrier structures having an extended end spaced from the base layer; and securing an adhesive layer to a surface of the base layer opposite the extended end of the barrier structures. 